Semiconductor device and method of manufacturing the same

ABSTRACT

A semiconductor device according to the present invention comprises a semiconductor substrate, a gate insulating film which is composed of a material whose main component is a tetravalent metal oxide, a mixture of a tetravalent metal oxide and SiO 2 , or a mixture of a tetravalent metal oxide and SiON and which containing B when it is in an nMOS structure on the semiconductor substrate or containing at least one of P and As when it is in a pMOS structure on the semiconductor substrate, and a gate electrode made of a metal having a work function of 4 eV to 5.5 eV.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is based upon and claims the benefit of priority fromthe prior Japanese Patent Application No. 2003-335966, filed Sep. 26,2003, the entire contents of which are incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to a semiconductor device which has a highdielectric constant thin film as an insulating film used for a gateinsulating film or the like and a metallic material as an electrode usedfor a gate electrode or the like and to a method of manufacturing thesemiconductor device.

2. Description of the Related Art

As LSIs have recently been getting much denser and much faster, elementsin LSIs have been miniaturized more. With the further miniaturization,there have been demands for silicon oxide (SiO₂) films to be made stillthinner in a capacitor and/or a transistor as component elements in aMOS structure. When the thickness of a SiO₂ film becomes as thin as 3 nmor less, electrons start to flow through a direct tunneling under anelectric field where the device operates, which causes the problem ofincreasing leakage current and therefore increasing the powerconsumption of the device and other problems.

To overcome the problems, a next-generation gate insulating filmreplaceable with the SiO₂ film has been desired and a high dielectricconstant film has been attracting attention. The reason is that a highdielectric constant film with the same capacitance as that of a SiO₂film is thicker than the latter. Making the insulating film thickermakes it possible to decrease the probability that electrons will tunnelthrough the insulating film or to suppress tunnel current to a lowlevel.

As a high dielectric gate insulating film replaceable with SiO₂, hafnium(Hf)-silicate has been nominated. In addition, to suppress the depletionin the gate electrode, it is desirable that the Hf-silicate should becombined with a metal gate-electrode for use.

However, it is difficult to produce a CMOS device using two types ofmetals with different work functions as a gate electrode by aconventional manufacturing method. The two types of work functions arepreferably equivalent to Fermi levels in widely-used poly-crystalline Sigate electrodes of the n-type and p-type MOSFET. In addition, one knownmethod of fabricating a CMOS device using one type of metal as a gateelectrode is to produce the difference between work functions byimplanting boron (B), phosphorus (P), arsenic (As) ions, or the likeinto nickel silicide (NiSi₂), followed by heat treatment. However, thedifference was about 0.5 V at most and therefore a sufficient valuecould not be obtained from the viewpoint of circuit design.

Jpn. Pat. Appln. KOKAI Publication No. 2002-280461 has disclosed amethod of introducing divalent or tetravalent metal impurities into atrivalent metal oxide to produce fixed charges and thereby causing aflat band voltage (V_(fb)) shift. As a result of experiments, in asystem using aluminum (Al) as trivalent metal and Hf as tetravalentmetal, the TDDB (time-dependent dielectric breakdown) deteriorated. Theresult has shown that the reliability deterioration was revealed whenthe introduced impurities were metals.

With the method of producing the difference between work functions inthe gate electrode by implanting B, P, As ions, or the like into nickelsilicide and then heat-treating the silicide, the difference in workfunctions between them was about 0.5 V at most and a sufficient valuecould not be obtained from the viewpoint of circuit design (e.g., seereference: J. Kedzierski et al., IEDM Tech., Dig. (2002) 247.

BRIEF SUMMARY OF THE INVENTION

According to an aspect of the invention, there is provided asemiconductor device comprising: a semiconductor substrate; a gateinsulating film which is composed of a material whose main component isa tetravalent metal oxide, a mixture of a tetravalent metal oxide andSiO₂, or a mixture of a tetravalent metal oxide and oxysilicon nitride(SiON) and which containing B when it is in an nMOS structure on thesemiconductor substrate or containing at least one of P and As when itis in a pMOS structure on the semi-conductor substrate; and a gateelectrode made of a metal having a work function of 4 eV to 5.5 eV.

According to another aspect of the invention, there is provided asemiconductor device manufacturing method comprising: forming a channelregion in a semiconductor substrate; forming on the channel region agate insulating film which is composed of a material whose maincomponent is a tetravalent metal oxide, a mixture of a tetravalent metaloxide and SiO₂, or a mixture of a tetravalent metal oxide and SiON;introducing B into the gate insulating film when the gate insulatingfilm is in an nMOS structure on the semiconductor substrate orintroducing at least one of P and As into the gate insulating film whenthe gate insulating film is in a pMOS structure; and forming on the gateinsulating film a gate electrode made of a metal having a work functionof 4 eV to 5.5 eV.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWING

FIGS. 1A and 1B are sectional views of a MOS structure showing a basicstructure of a semiconductor device according to an embodiment of thepresent invention and FIGS. 1C and 1D are basic characteristic diagramsof the semiconductor device;

FIG. 2 is a sectional view showing a process of manufacturing asemiconductor device according to a first embodiment of the presentinvention;

FIG. 3 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 4 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 5 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 6 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 7 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 8 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 9 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 10 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 11 is a sectional view showing a process of manufacturing thesemiconductor device of the first embodiment;

FIG. 12 is a sectional view showing a process of manufacturing asemiconductor device according to a second embodiment of the presentinvention;

FIG. 13 is a sectional view showing a process of manufacturing thesemiconductor device of the second embodiment;

FIG. 14 is a sectional view showing a process of manufacturing thesemiconductor device of the second embodiment;

FIG. 15 is a sectional view showing a process of manufacturing thesemiconductor device of the second embodiment;

FIG. 16 is a sectional view showing a process of manufacturing asemiconductor device according to a third embodiment of the presentinvention;

FIG. 17 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 18 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 19 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 20 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 21 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 22 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 23 is a sectional view showing a process of manufacturing thesemiconductor device of the third embodiment;

FIG. 24 is a sectional view showing a process of manufacturing asemiconductor device according to a fourth embodiment of the presentinvention;

FIG. 25 is a sectional view showing a process of manufacturing thesemiconductor device of the fourth embodiment;

FIG. 26 is a sectional view showing a process of manufacturing thesemiconductor device of the fourth embodiment;

FIG. 27 is a sectional view showing a process of manufacturing thesemiconductor device of the fourth embodiment;

FIG. 28 is a sectional view showing a process of manufacturing thesemiconductor device of the fourth embodiment;

FIG. 29 is a sectional view showing a process of manufacturing thesemiconductor device of the fourth embodiment;

FIG. 30 is a sectional view showing a process of manufacturing thesemiconductor device of the fourth embodiment;

FIGS. 31A and 31B are sectional views of a MOS structure showing a basicstructure of a semiconductor device according to a modification of eachof the first to fourth embodiments;

FIGS. 32A and 32B are sectional views of an nMOS structure showing abasic structure of a semiconductor device according to a modification ofeach of the first to fourth embodiments;

FIG. 33 is a sectional view showing a process of manufacturing asemiconductor device according to a fifth embodiment of the presentinvention;

FIG. 34 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 35 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 36 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 37 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 38 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 39 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 40 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment;

FIG. 41 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment; and

FIG. 42 is a sectional view showing a process of manufacturing thesemiconductor device of the fifth embodiment.

DETAILED DESCRIPTION OF THE INVENTION

Hereinafter, referring to the accompanying drawings, embodiments of thepresent invention will be explained.

FIGS. 1A and 1B are sectional views of a MOS structure showing a basicstructure of a semiconductor device according to an embodiment of thepresent invention. FIG. 1A shows the structure of an nMOS (n-channelMOSFET) and FIG. 1B shows the structure of a pMOS (p-channel MOSFET).Although each of FIGS. 1A and 1B shows a MOS capacitor structure,providing the. MOS capacitor structure with a source and a drain enablesthe structure to be applied to a transistor.

In a surface of semiconductor substrate 101 made of Si or the like, achannel region 103 or 104 is formed. On the channel region, a gateinsulating film 105 made of Hf-silicate (HfSiO) or the like is formed.On the gate insulating film 105, a metal gate electrode 115 is formed.In the electrode side of the gate insulating film 105, a layer 105 bwith positive fixed. charges is formed in the nMOS and a layer 105 cwith negative fixed charges is formed in the pMOS.

The gate insulating film 105 contains at least one of metal oxide, metalnitride, and metal oxynitride. For example, the gate insulating film 105contains a material whose main component is tetravalent metal oxide, amixture of tetravalent metal oxide and SiO₂ ((MO₂)_(X)(SiO₂)_(1-X):0<x≦1, where M is tetravalent metal), or a mixture of tetravalent metaland SiON. The metal includes titanium (Ti), zirconium (Zr), and Hf. Forexample, the material contains Hf-silicate composed of Hf, Si, O, and N.In addition, the material may contain Zr-silicate (ZrSiO), ZrSiON,HfZrSiO, HfZrSiON, HfAlO, HfAlON, HfZrAlO, HfZrAlON, HfSiAlON, orHfZrSiON. There is a possibility that the inclusion of trivalent metalAl will permit fixed charges to be induced. However, the fixed chargeeffect of the gate insulating film will not be lost completely even inthe presence of fixed charge caused by other elements, since theembodiment is characterized by containing tetravalent metals Hf, Zr andtrivalent nonmetals B, P, As. As a film forming method for, for example,Hf-silicate as a gate insulating film, any one of vacuum evaporation,sputtering techniques, zol-gel techniques, laser abrasion techniques,and CVD techniques may be used. For instance, in the CVD techniques, thefilm can be formed, by supplying TEOS (Si(OC₂H₅)₄), HTB (Hf(OC(CH₃)₃)₄),and O₂ simultaneously at 600° C. and 1 Toor. The composition ratioHf/(Hf+Si) can be controlled by adjusting the amount of TEOS and HTBsupplied. The film thickness can be controlled by adjusting the supplytime. When the Hf/(Hf+Si) ratio in the vicinity of the electrode of thegate insulating film is 1% or more, the effect of a shift in thethreshold voltage by fixed charges can be expected sufficiently.Thereafter, heat treatment is performed for five minutes in anatmosphere of NH₃ at 800° C. and 100 Torr, which enables N to beintroduced into Hf-silicate.

The material for the metal gate electrode 115 may be made not only of asingle type of metal, such as Fe, Co, Ni, Ti, Hf, or Zr but also of analloy of these metals. As long as the material has a metallic electricalcharacteristic, it may contain Si, Ge, N, B, P, As, or the like. Forinstance, the material may be such silicide as HfSi₂ or CoSi₂ or such anitride as TiN. For example, when the gate insulating film isHf-silicate, it is desirable that such metallic material as HfSiN shouldbe selected as a material common to the gate electrode of bothstructures to stabilize the characteristics, taking into account thediffusion of the gate electrode material and the gate insulating filmmaterial during the heat treatment in the LSI manufacturing processes.

When the fixed charge layers 105 b, 105 c are formed in the gateinsulating films 105, B, P, As, or the like may be used as additionalelements. Furthermore, elements that produce positive fixed chargesinclude Al, Ga, In, and Tl in the 3B group to which B belongs andelements that produce negative charges include N, Sb, and Bi in the 5Bgroup to which P and As belong. Other materials can produce a similareffect, as long as they enable fixed charges to be produced in the gateinsulating films.

FIGS. 1C and 1D show the basic characteristics of semiconductor devicesaccording to the embodiment. FIG. 1C shows flat band voltages V_(fb)obtained when Hf-silicate films with a film thickness of 4 nm, 7 nm, and10 nm in the composition ratio Hf/(Hf+Si)=30% were formed as a gateinsulating film on an n-type Si substrate and polycrystalline Si wasused as a gate electrode. FIG. 1D shows flat band voltages V_(fb) in thecase of a p-type Si substrate under the same conditions. FIGS. 1C and 1Dalso show a case where SiO₂ was produced in the form of a gateinsulating film in the same manufacturing processes as reference. TheV_(fb) of Hf-silicate depends slightly on the film thickness. Thedifference between the V_(fb) of Hf-silicate and the V_(fb) of SiO₂indicates existence of fixed charges in the vicinity of the Si gateelectrode in the Hf-silicate layer.

In the case of B in FIG. 1C, V_(fb) is shifted about 0.6 to 0.7 V in thenegative direction, producing positive fixed charges. In the case of Pand As in FIG. 1D, V_(fb) is shifted about 0.2 to 0.3 V in the positivedirection, producing negative fixed charges. With this composition, thethreshold values of nMOS and pMOS will be balanced well, when such amaterial is selected as the gate electrode which has a work functionshifted about 0.2 V toward the valence band from the mid-gap of the Sisubstrate. In the embodiment, the gate electrode is made of metal with awork function of, for example, 4 to 5.5 eV.

Since the amount of fixed charges depend on the composition of the gateinsulating film and the amount of B, P, and As introduced therein, forexample, the Hf/(Hf+Si) ratio may be increased when more fixed chargesare needed.

In the embodiment, before the formation of the insulating film, a thinfilm can be formed for example, an SiON layer of about 0.6 nm thick, onthe underlying substrate (e.g., Si) to prevent B, P, and As diffusingfrom the gate insulating film to the substrate. To form fixed chargessufficiently, as many impurities as possible should be added to the gateinsulating film. However, the change of the impurity concentration inthe channel region can cause variations in the threshold values of nMOSand pMOS or make the device design complicated. To avoid the problems,the thin film, e.g. SiON, is used to prevent B, P, and As diffusing intothe substrate during heat treatment in the LSI manufacturing processes.

Moreover, the embodiment also includes a process of diffusing B from theupper side of the insulating film containing Hf(Zr) in the nMOS and atleast one of P and As from the upper side of the insulating film in thepMOS and a process of forming a metal gate electrode (including silicideor nitride) on the insulating film.

FIGS. 2 to 11 are sectional views showing the processes of manufacturinga semiconductor device according to a first embodiment of the presentinvention. Although FIGS. 2 to 11 shows the embodiment related to a pairof nMOS and pMOS, they are not necessarily arranged side by side on asingle substrate. Of course, the first embodiment may be applied to anSOI (Silicon On Insulator) MOSFET and a vertical MOS (with a channelperpendicular to the substrate surface and electrons and holes movingalong the channel, or perpendicularly to the substrate surface).

First, as shown in FIG. 2, after an SiO₂ film 202 for trench isolationis formed in an Si substrate 201, the substrate 201 is covered with aresist in which openings are selectively made only on the device regionsby photolithography, thereby forming channel regions 203 a, 204 a intowhich necessary dopant has been implanted.

Next, as shown in FIG. 3, an Hf-silicate layer 205 a is formed as a gateinsulating film. TEOS (Si(OC₂H₅)₄), HTB (Hf(OC(CH₃)₃)₄), and O₂ aresupplied simultaneously at 600° C. and 1 Toor by CVD techniques, whichenables Hf-silicate to be deposited to a thickness of about 4 nm withHf/(Hf+Si) ratio=30%.

Next, B, P, or As is introduced into the electrode side of theHf-silicate layer 205 a. For example, this is done as follows. After theHf-silicate film is formed, an Si layer 206 a is deposited on theHf-silicate layer 205 a to a thickness of 50 nm at 620° C. in a mixedgas of SiH₄, N₂, and H₂. The layer 206 a is covered with a resist 207 inwhich openings are selectively made only on the device regions byphotolithography, which enables B ions to be selectively implanted intoa Si layer 206 b on the region to become the gate insulating film in thenMOS and at least one of P and As ions to be selectively implanted intoa Si layer 206 c on the region to become the gate insulating film in thepMOS as shown in FIG. 4.

Then, as shown in FIG. 5, a rapid thermal annealing (RTA: short-timehigh-temperature annealing) is performed, thereby diffusing B, P, or Asinto the Hf-silicate film. The acceleration voltage in the ionimplantation should be selected at a level that does no damage to theHf-silicate layer during implantation. For instance, B ions areimplanted at about 2 keV, P ions are implanted at about 5 keV, and Asions are implanted at about 20 keV. The dose amount is adjusted so as tobe about 1×10²⁰ cm⁻³ or 1×10¹³ cm⁻² in the vicinity of the interfacebetween the Hf-silicate layer 205 a and Si layer 206 b and of theinterface between the Hf-silicate layer 205 a and Si layer 206 c duringthe diffusion to be carried out next. Therefore, the dose amount dependson the diffusion condition. For instance, diffusion is performed by heattreatment for about three seconds at 1000° C. with a dose of 1×10¹⁵cm⁻². As a result, in the vicinity of the electrode of the Hf-silicatelayer 205 a, a layer 205 b with positive charges is formed in the nMOSand a layer 205 c with negative charges is formed in the pMOS. The Silayers 206 b, 206 c need not be adjusted to the gate length. If thediffusion time is made longer and more B, P, or As are implanted, the Silayers 206 b, 206 c may have a shorter length than the gate length. Ifthe uniformity of the fixed charge layers 205 b, 205 c along the gatelength direction is taken seriously, the Si layers 206 b, 206 c may havea longer length than the gate length.

Next, as shown in FIG. 6, an Si layer 208 a is deposited to a thicknessof 100 nm at 620° C. in a mixed gas of SiH₄, N₂, and H₂. Then, as shownin FIG. 7, with a resist patterned by photolithography techniques, theSi layers 206 a, 208 a are etched into a gate electrode shape by areactive ion etching (RIE). Thereafter, using a solution containing HF,the Hf-silicate layer 205 a is processed.

Next, as shown in FIG. 8, after an SiO₂ film is deposited on the entiresurface, the entire surface is etched back by RIE, thereby forming agate sidewall SiO₂ film 209 with a thickness of 5 nm. Then, with the Silayers 208 b, 208 c and the sidewall SiO₂ layer 209 as a mask, at leastone of P and As is implanted with a dose of 1×10¹⁵ cm⁻² at anacceleration voltage of 20 keV in the nMOS and B is implanted with adose of 1×10¹⁵ cm⁻² at an acceleration voltage of 2 keV in the pMOS.

Next, as shown in FIG. 9, RTA is performed for one second at 1000° C.,thereby forming sources and drains 203 b, 203 c, 204 b, 204 c. At thistime, to prevent the effect of the fixed charges in the fixed chargelayer 205 b region from being lost due to the diffusion of P or As fromthe Si layer 208 b or the dissociation of B from the fixed charge layer205 b through the Si layer 206 b, it is desirable that RTA should beperformed as short as possible. Similarly, attention should be given tothe fixed charges in the fixed charge layer 205 c region because of thediffusion of B from the Si layer 208 c or the dissociation of P or Asfrom the fixed charge layer 205 c through the Si layer 206 c.

Next, as shown in FIG. 10, after Co is deposited, CoSi₂ layers 210 a,210 b, 211 a, 211 b are formed on the sources and drains by carrying outheat treatment and removing the remaining Co. At the same time, the Silayers 206 b, 206 c, 208 b, 208 c are turned into silicide, therebyforming metal gate electrodes 206 d, 206 e, 208 d, 208 e.

Next, as shown in FIG. 11, an interval insulating film SiO₂ layer 212using TEOS or the like is deposited on the entire surface. Contact holesare made so as to connect to the sources and drains. Then, Al/TiN/Ti orCu/TiN/Ti wiring layers 213 a, 213 b, 213 c, 213 d are formed.

From this step on, wiring processes for a second and later layers arecarried out, which completes the LSI.

FIGS. 12 to 15 are sectional views showing the processes ofmanufacturing a semiconductor device according to a second embodiment ofthe present invention.

First, as shown in FIG. 12, on an Si substrate 301, isolations 302,channel regions 303 a, 304 a, and a gate insulating film (Hf-silicatelayer) 305 a are formed. The method is the same as in the firstembodiment.

Next, B, P, As, or the like is introduced into the electrode side of thegate insulating film 305 a. The gate insulating film 305 a is coveredwith a resist 307 in which openings are selectively made in the regionsto eventually become gate insulating film parts by photolithography.Next, in the nMOS, B is selectively implanted with a dose of 1×10¹³cm⁻². In the pMOS, at least one of P or As is selectively implanted witha dose of 1×10¹³ cm⁻². The acceleration voltage is low so as to preventthe Hf-silicate layer from being damaged during implantation. Forexample, B is implanted at about 200 eV, P is implanted at about 500 eV,and As is implanted at about 2 keV. In addition, thermal evaporationdeposition techniques may be used. Then, for annihilation of the damage,an annealing is done at 800° C. for 30 seconds in an atmospherecontaining O₂.

Next, as shown in FIG. 13, an Si layer 306 a is deposited to a thicknessof 150 nm at 620° C. in a mixed gas of SiH₄, N₂, and H₂. Then, as shownin FIG. 14, with a resist patterned by photolithography as a mask, theSi layer 306 a is processed into a gate electrode shape by RIE.Thereafter, using a solution containing HF, the Hf-silicate layer 305 ais processed.

Next, as shown in FIG. 15, after another SiO₂ film is deposited on theentire surface, the entire surface is etched back by RIE, therebyforming a gate sidewall SiO₂ film 309 with a thickness of 5 nm. Then,with the Si layers 306 b, 306 c and the sidewall SiO₂ layer 309 as amask, As is implanted with a dose of 1×10¹⁵ cm⁻² at an accelerationvoltage of 20 keV in the nMOS and B is implanted with a dose of 1×10¹⁵cm⁻² at an acceleration voltage of 2 keV in the pMOS.

From this step on, the formation of the sources and drains by one secondof RTA at 1000° C., the formation of a CoSi₂ layer, wiring processes,and others are the same as in the first embodiment.

FIGS. 16 to 23 are sectional views showing the processes ofmanufacturing a semiconductor device according to a third embodiment ofthe present invention.

First, as shown in FIG. 16, on an Si substrate 401, isolations 402,channel regions 403 a, 404 a,, and a gate insulating film (Hf-silicatefilm) 405 a are formed. The method is the same as in the firstembodiment. Next, an Si layer 406 a is deposited to a thickness of 150nm at 620° C. in a mixed gas of SiH₄, N₂, and H₂.

Then, as shown in FIG. 17, with a resist patterned by photolithographyas a mask, the Si layer 406 a is processed into a gate electrode shapeby RIE. Thereafter, using a solution containing HF, the Hf-silicatelayer 405 a is processed.

After an SiO₂ film is deposited on the entire surface, the entiresurface is etched back by RIE, thereby forming a gate sidewall SiO₂ film409 with a thickness of 5 nm. Then, with the Si layer 406 a and thesidewall SiO₂ layer 409 as a mask, As is implanted with a dose of 1×10¹⁵cm⁻² at an acceleration voltage of 20 keV in the nMOS and B is implantedwith a dose of 1×10¹⁵ cm⁻² at an acceleration voltage of 2 keV in thepMOS.

Next, as shown in FIG. 18, an interlevel insulating film SiO₂ 412 usingTEOS or the like is deposited on the entire surface. Then, as shown inFIG. 19, not only the SiO₂ layer 412 but also the Si layers 414 b, 414 care removed by CMP. Then, as shown in FIG. 20, the resulting film iscovered with a resist in which openings are selectively made only on thedevice regions by photolithography. In this state, B is selectivelyimplanted into Si on the region which will eventually become a gateinsulating film in the nMOS and at least one of P and As is selectivelyimplanted in the pMOS.

Then, as shown in FIG. 21, RTA is performed, thereby diffusing B, P, orAs into the Hf-silicate. The acceleration voltage is at a level thatdoes no damage to the Hf-silicate layer during implantation. Forinstance, B ions are implanted at about 2 keV, P ions are implanted atabout 5 keV, and As ions are implanted at about 20 keV. The dose amountis adjusted so as to be about 1×10²⁰ cm⁻³ or 1×10¹³ cm⁻² in the vicinityof the interface between the Hf-silicate layer 405 a and Si layer 406 band of the interface between the Hf-silicate layer 405 a and Si layer406 c during the diffusion to be carried out next. Therefore, the doseamount depends on the diffusion condition. For instance, diffusion isperformed by heat treatment for about three seconds at 1000° C. with adose of 1×10¹⁵ cm⁻². As a result, in the vicinity of the electrode ofthe Hf-silicate layer 405 a, a layer 405 b with positive charges isformed in the nMOS and a layer 405 c with negative charges is formed inthe pMOS.

Next, as shown in FIG. 22, the Si layers 406 b, 406 c are removed byCDE. Then, as shown in FIG. 23, after TiN is deposited on the entiresurface by sputtering techniques, the deposited TiN is covered with aresist processed into a gate electrode shape by photolithography andthen is etched with an H₂O₂-contained solution. This completes a metalgate electrode 415.

From this step on, the subsequent processes, including wiring processes,are the same as in the first embodiment.

FIGS. 24 to 30 are sectional views showing the processes ofmanufacturing a semiconductor device according to a fourth embodiment ofthe present invention.

First, the gate insulating film of each of an nMOS and a pMOS isprovided with a fixed charge layer by damascene techniques as follows.In an Si substrate 501, isolations 502, channel regions 503 a, 504 a areformed. The method is the same as in the first embodiment. Next, an SiO₂layer 516 is formed to a thickness of 5 nm at 800° C. in anO₂-containing atmosphere. The SiO₂ layer 516 may be formed by CVDtechniques using TEOS. Alternatively, the Hf-silicate or the like may besubstituted for the SiO₂ layer 516. Then, an Si layer 506 a is depositedto a thickness of 150 nm at 620° C. in a mixed gas of SiH₄, N₂, and H₂.

Next, as shown in FIG. 25, with a resist patterned by photolithographyas a mask, the Si layer 506 a is processed into a gate electrode shapeby RIE. Thereafter, using a solution containing HF, the SiO₂ layer 516is processed.

After another SiO₂ film is deposited on the entire surface, the entiresurface is etched back by RIE, thereby forming a gate sidewall SiO₂ film509 with a thickness of 5 nm. Then, with the Si layer 506 a and thesidewall SiO₂ layer 509 as a mask, As is implanted with a dose of 1×10¹³cm⁻² at an acceleration voltage of 20 keV in the nMOS and B is implantedwith a dose of 1×10¹³ cm⁻² at an acceleration voltage of 2 keV in thepMOS. A source and a drain are formed by RTA for three seconds at 1000°C.

Next, as shown in FIG. 26, an interlevel insulating film SiO₂ 512 usingTEOS or the like is deposited on the entire surface. Then, the surfacesof the Si layers 508 b, 508 c are exposed by CMP. Then, as shown in FIG.27, after the Si layers 508 b, 508 c are removed by RIE, the SiO₂ layer512 is removed with a solution containing HF.

Next, as shown in FIG. 28, a gate insulating film (Hf-silicate layer)505 a is formed by the aforementioned method. Then, as shown in FIG. 29,the gate insulating film is covered with a resist in which openings areselectively made in the gate electrode regions by photolithography. Inthis state, B is selectively implanted into Si on the region which willeventually become a gate insulating film in the NMOS and at least one ofP and As is selectively implanted in the pMOS. The regions in whichopenings are made are not necessarily limited to the gate electroderegion and may be made larger than the electrode regions by use of theregions where the interlevel insulating film SiO₂ 512 is present, whichprevents misalignment.

Next, as shown in FIG. 30, after TiN is deposited on the entire surfaceby sputtering techniques, the deposited TiN is covered with a resistprocessed into a gate electrode shape by photolithography and then isetched with an H₂O₂-contained solution. This completes a metal gateelectrode 515.

From this step on, the subsequent processes, including wiring processes,are the same as in the first embodiment.

FIGS. 33 to 42 are sectional views showing the processes ofmanufacturing a semiconductor device according to a fifth embodiment ofthe present invention.

First, as shown in FIG. 33, on an Si substrate 901, isolations 902,channel regions 903 a, 904 a, and a gate insulating film 905 a areformed. The method is the same as in the first embodiment.

Next, an Si layer 906 a is deposited to a thickness of 150 nm at 620° C.in a mixed gas of SiH₄, N₂, and H₂. Then, the Si layer 906 a is coveredwith a resist in which openings are selectively made only on the deviceregions by photolithography. In this state, B is selectively implantedinto Si on the region which will eventually become a gate insulatingfilm in the nMOS and at least one of P and As is selectively implantedin the pMOS. Under the conditions that the amount of dopant reaching thechannel region is less than the dopant concentration in the channelregion, the acceleration voltage at that time should be set as high aspossible so that the dopant gets closer to the gate insulating film(Hf-silicate layer) 905 a. For example, As is implanted with a dose of1×10¹⁵ cm⁻² at an acceleration voltage of 50 keV and B is implanted witha dose of 1×10¹⁵ cm⁻² at an acceleration voltage of 8 keV.

Next, as shown in FIGS. 34 and 35, with a resist patterned byphotolithography as a mask, the Si layer 906 a is processed into a gateelectrode shape by RIE. Thereafter, using a solution containing HF, thegate insulating film 905 a is processed. Then, after another SiO₂ filmis deposited on the entire surface, the SiO₂ film is etched back by RIE,thereby forming a gate sidewall SiO₂ film 909 with a thickness of 5 nm.

Then, as shown in FIG. 37, with the Si layer 906 b and the sidewall SiO₂layer 909 as a mask, As is implanted with a dose of 1×10¹⁵ cm⁻² at anacceleration voltage of 1 keV in the nMOS and B is implanted with a doseof 1×10¹⁵ cm⁻² at an acceleration voltage of 0.2 keV in the PMOS. It isdesirable that the regions 908 b, 908 c into which ions are implanted atthat time should be made as thin as possible in the upper part of theregions 906 b, 906 c formed at the prior ion implantation.

Next, as shown in FIG. 38, RTA is performed at 1000° C. for one secondto diffuse dopant into the gate insulating film 905 a, thereby formingregions 905 b, 905 c containing B and As. At the same time, sources anddrains 903 b, 903 c, 904 b, 904 c are electrically activated. At thistime, it is desirable that the annealing time of RTA should be as shortas possible so that the dopant in the regions 908 b, 908 c may not reachthe regions 905 b, 905 c, respectively.

From this step on, the subsequent processes, including the formation ofthe CoSi₂ layer shown in FIG. 39 and wiring processes in FIG. 40, arethe same as in the first embodiment.

Furthermore, as shown in FIG. 41, a layer 906 f to suppress thediffusion of dopant in activation RTA may be provided in the Si layer906 a. In this case, it is desirable not to disturb the process offorming metal gate electrodes 906 d, 906 e, 908 d, 908 e from the Silayer 906 a shown in FIG. 39, if possible. For example, after the Silayer 906 a is formed to a thickness of 80 nm by the aforementionedmethod, it is heat-treated at about 800° C. or lower in anoxygen-containing atmosphere, thereby producing an oxidized-Si-layerwith a thickness of about 0.3 nm to 1 nm as the region 906 f. Then, anSi layer 906 a is formed to a thickness of 70 nm by the aforementionedmethod. As shown in FIG. 42, the layer 906 f prevents dopant in theregions 908 b, 908 c from diffusing and reaching the regions 905 b, 905c, which enables the activation of source and drain, as shown in FIG.38, at higher temperature than 1000° C. and for a longer time than onesecond.

Hereinafter, modifications of the first to fifth embodiments will beexplained. The first to fifth embodiments may be used independently orcombined suitably. In addition to this, they may be combined with any ofthe methods explained below.

FIGS. 31A and 31B are sectional views of a MOS structure showing thebasic structure of a semi-conductor device according to a modificationof the embodiments. FIG. 31A shows an nMOS structure and FIG. 31B showsa pMOS structure.

As shown in FIG. 31A, a B-contained Si layer 617 b with a thickness ofabout 0.3 nm to 3 nm may be provided between a gate insulating film 605b with fixed charges produced by the inclusion of B and a metal gateelectrode 615. Since the metal layer 615 has a higher free electrondensity than that of the Si layer 617 b, making the Si layer 617 b to athickness of about 3 nm or less causes the metal layer 615 to bedominant as a gate electrode. The Si layer 617 b can prevent B fromdiffusing from the gate insulating film 605 b into the metal gateelectrode 615 in manufacturing LSIs and also preventing the fixedcharges to decrease and the threshold value to change.

When CoSi₂ or NiSi₂ is used as the metal gate electrode 615, the Silayer 617 b prevents Co or Ni from diffusing into the gate insulatingfilm 605 b and degrading the reliability of the gate insulating film 605a.

Similarly, as shown in FIG. 31B, in pMOS, in place of the Si layer 617b, an Si layer 617 c containing one of P and As which is contained inthe gate insulating film with fixed charges may be provided.

Furthermore, when the gate insulating films 205 b, 205 c with fixedcharges are formed as shown in FIGS. 2 to 11, not only the ionimplantation method but also EB techniques or thermal evaporation may beused to form the Si layers 206 b, 206 c containing B, P, As, or thelike. When the Si layer is formed, it may be formed by supplying SiH₄together with BH₃, PH₃, and AsH₃.

FIGS. 32A and 32B are sectional views of an nMOS structure showing thebasic structure of a semi-conductor device according to a modificationof the embodiments.

In nMOS of FIG. 32A, as a method for forming a gate insulating film 715b with fixed charges as shown in FIG. 32B, after forming a gateinsulating film 705 a and a metal gate electrode 715, B is implantedmainly into the vicinity 705 b of the gate insulating film 705 a in themetal gate electrode 715, and then the resulting film is heat treated toform the gate insulating film 715 b. In the PMOS, P or As is implantedin place of B.

As described above, with the embodiments, when the gate insulating filmcontaining Hf(Zr) contains B in the vicinity of its gate electrode inthe nMOS and at least one of P and As in the vicinity of its gateelectrode in the pMOS and the gate electrode contains a metal with awork function near the mid-gap, this makes it possible to obtain a largedifference in work function between the gate electrode in the nMOS andthat in the pMOS. At this time, making use of the fact that B producespositive fixed charges and P or As produces negative charges in the gateinsulating film, the threshold voltage of nMOS and that of pMOS arechanged. This enables a CMOS to be produced using one type of metalcommon to nMOS and pMOS as a gate electrode. Furthermore, thereliability can be maintained higher than in a case where metal impurityis introduced instead of P, As, or B as disclosed in Jpn. Pat. Appln.KOKAI Publication No. 2002-280461.

According to the embodiments of the present invention, it is possible toprovide a semiconductor device with low threshold voltages which usesone type of metal for the gate electrodes of nMOS and pMOS and a methodof manufacturing the semiconductor device.

Furthermore, B is introduced into a part or all of a silicate-based gateinsulating film containing hafnium or zirconium, or both hafnium andzirconium in the nMOS structure on a semiconductor substrate, and atleast one of P and As is introduced similarly in the pMOS structure,thereby providing a region with fixed charges, which makes it easy todesign a circuit using a CMOS having one kind of metal gate electrode.In addition, for example, when nonmetal P, As, or B was introduced intoan HfSiO-based material, the deterioration in TDDB was not observed.That is, it is possible to keep the reliability higher than in a casewhere metal impurity is introduced instead of P, As, or B as disclosedin Jpn. Pat. Appln. KOKAI Publication No. 2002-280461.

In addition, this invention may be practiced or embodied in still otherways without departing from the spirit or essential character thereof.

Additional advantages and modifications will readily occur to thoseskilled in the art. Therefore, the invention in its broader aspects isnot limited to the specific details and representative embodiments shownand described herein. Accordingly, various modifications may be madewithout departing from the spirit or scope of the general inventionconcept as defined by the appended claims and their equivalents.

1-4. (canceled)
 5. A semiconductor device comprising: a semiconductorsubstrate; a gate insulating layer which is provided on thesemiconductor substrate, and which is comprised of a first insulatorincluding a metal element; a fixed charge element layer which isprovided on the gate insulating layer, and which is comprised of asecond insulator including a fixed charge element with a fixed charge;and a gate electrode which is provided on the fixed charge elementlayer.
 6. The semiconductor device according to claim 5, furthercomprising a Si layer which is provided between the fixed charge elementlayer and the gate electrode.
 7. The semiconductor device according toclaim 6, wherein the Si layer includes the fixed charge element.
 8. Thesemiconductor device according to claim 7, further comprising a layerwhich is provided between the Si layer and the gate electrode, and whichprevents an element in the gate electrode from diffusing.
 9. Thesemiconductor device according to claim 5, wherein the metal element isa tetravalent metal element.
 10. The semiconductor device according toclaim 5, wherein each of the first and second insulators is one selectedfrom a group of oxide, nitride, and oxynitride.
 11. The semiconductordevice according to claim 5, wherein the fixed charge element is oneselected from a group of B, Al, Ga, In, and TI, when a p-MOS structureis comprised of the semiconductor substrate, the gate insulating filmand the gate electrode.
 12. The semiconductor device according to claim5, wherein the fixed charge element is one selected from a group of P,As, N, Sb, and Bi, when a n-MOS structure is comprised of thesemiconductor substrate, the gate insulating film, and the gateelectrode.
 13. The semiconductor device according to claim 5, whereinthe first insulator is the same as the second insulator.
 14. Thesemiconductor device according to claim 13, wherein the first and secondinsulators include the metal element selected from a group of Ti, Hf,and Zr.
 15. The semiconductor device according to claim 5, wherein thegate electrode includes a metal element selected from a group of Fe, Co,Ni, Ti, Hf, and Zr.
 16. The semiconductor device according to claim 15,wherein the gate electrode includes a dopant selected from a group ofSi, Ge, N, B, P, and As.
 17. The semiconductor device according to claim5, wherein the gate electrode includes Hf and Si, when the first andsecond insulators include Hf and Si.
 18. The semiconductor deviceaccording to claim 5, wherein the gate electrode is comprised of amaterial having a work function of 4 eV to 5.5 eV.
 19. The semiconductordevice according to claim 5, wherein the semiconductor substrate has aSOI structure.